Disubstituted guanidine salts of metalliferous azo dyes



Patented J i '1939 PATENT OFFICE msuns'rrru'ran omsmms sun's or sm'rmmesous AZO nras Herbert w. Daudt and 01mm w. llannumpwilmington, Del., assignors Nemours a Company. Wilmi poratlon of Delaware to E. I. du Pont de nston, Del. a cor- No Drawing. Application July 14, 1987. Serial No. 158,515

new. (Cl. zoo-1m s The products of that patent have many excellent properties among which is solubility in alcohol and similar common organic solvents, but they are somewhat lacking in iastness to light.

It is an object 01' this invention to produce azo 10 dyes which are soluble in common organic solvents, which are of desirable shade. or excellent brightness, which have afllnity for leather, wood, pyroxylin, and paper, and which are stable to light.

'I'he objects oi the invention are accomplished, generally speaking, by making and using di-substitute'd guanidine salts oi metalliterous azo dyes having at least one water-solubilizing group, such as 0001-! or 8011! and having a metal in the range atomic weight 51.9 to 64.0, inclusive.

In the practice of the preferred form 0! the invention an and dye, having a sulionic or carboxylic acid substituent and having an hydroxy ortho to azo, and which may have'hydroxy ortho to a carboxy group, and which may have hydroxy groups present in other positions, is metallized with copper or chromium, or with-one of the othermetals appearing in the range described, is dissolved in a substantially neutral aqueoussolution, and is reacted with a di-substituted guanidine-which is preferably a di-aryl',guanidine,' in .whichthej dye used as a starting must comprise a metallii'erous product obtainedby a previous introduction of. the metal into an azo dye which contains or carbony groups in a position adjacent to M0 group or an ortho'tola carbonyl group, and must contain one or more like or unlike azo' groups, and must contain one or more sol'ubilizing groups such as sulionio orcarboxylie acid... t In addition to the metals which have been named nickel, cobalt, manganese, andiron the ot particular value and their atomic weights lie in the above range. The preferred metals, chromium and copper, are members oi groups 6 and 16, respectively, oi the periodic system. I The metaliiierous dyes are preferably used in the iorm 01' their neutral aqueous solutions. Alkaline solution will cause the separation of undue amounts of the di-substituted guanidine during the formation of the til-substituted, guanidine salt.

The di-substituted guanidines ma be brine aryi, alkyharalkyhotcyclohexyl series. They tate and hydrochloride.

may be symmetrical or unsymmetrical. The alkyl group preferably contains from 4 to 10 carbon atoms. They are usually used in the form 01 their neutral salts, such as the tomato, ace- I Other-water soluble s salts will usually sufllee- The preferred di-substituted guanidines are the diaryl guanidinea'such' as di-(ortho-tolynguanidine', di-(para-phenetyDguanidine, di-(ortho-anisyDguanidine' and di-xylyl guanidine.

.The relative proportions of dye and substituted guanidine may vary over a wide range, depending upon the number of acid groups in the dye, the number of acidic groups to be reacted with the guanidine, and the degree 01 hydrolysis and solubility of the product. The amount of the guanidine salt should be at least equivalent to one acid group; preferably, an excess is used.

It does not necessarily follow that an excess of the guanidine salt will cause a reaction to take place between the guanidine and all 01' the acidic groups (SOaH, etc.),.

The temperature conditions, under which the dye and the g'uanidine salt are mixed and the conditions subsequently imposed upon the mixture, have varied with the formation of different products. lnsome caseaexcellent' results have been obtained by conductingfthemixing operation at -25 C. and subsequently filtering at the same temperature; in other cases, subsequent heating to fill- C. was necessary for the rapid filtration of the product.

The following examples illustrate the processes and the products, but are not limitative oi the invention: 2

Twenty parts of a dye, consisting of a commercially available chromed complex of the ass combination, formed by the interaction of diazotized l-amino 2-naphthol-4-sulionic acid with 1- (4 -suifo-phenyl) -3-methyl-5-pyrazolone, was dissolved in 400 parts oi water; the solution was filtered. The filtered solution was stirred at room temperature while 100 parts or a 11% neu- 4.1 tral solution 0! di-ortho-tolyl-guanidine-hydrochloride was added. A red precipitate formed immediately. The mass was heated to 60-65 6., cooled to 35 and then filtered. The residue was washed with a eold 1% solution of di-ortho tolyl- .guanidine and subsequently with a limited amount of water. The'residue was dried at approximately sore.v

. The dried product was soluble inalcoholand in similar solvents. Its solutions were of a 5 slightly bluish-red color. They were used for the dyeing and staining of paper, wood, and leather.

The dyed and stained materials were 01' a rich, bright bluish-red color. This dye, applied to these materials, was inappreciabiy aflected by 53 hours of exposure to a iadometer. On the other hand. a number of commercial dyes, similarly applied and giving similar shades, were markedly aflected by 8% hours of the same exposure. These commercial dyes consisted of the di-ortho-tolyl-guaiudine salts of non-metal am dyes.

Example If Seven parts of the coppered complex oi th azo combination, prepared from two mole of diazotized anthranilic acid and one moi of Rhoduline acid, was dissolved in 450 parts of water, and e resulting solution filtered. The filtered solution was stirred and treated with 10 parts of a solution (11%) 01 di-ortho-tolyl-guanidine hydrochloride until no further precipitation or insoluble material could be observed. The precipitate was removed by filtration at room temperature. The residue was washed with a 1% di ortho-tclyl-guanidine hydrochloride solution, and finally with a limited amount or water. It was then dried at room temperature.

The dried product consisted of dark violet lumps, which were ground to a powder. This product was then allowed to stand at room temperature. After several days it had solidified. It was then ground to a red powder.

This product was soluble in alcohol and in similar solvents, it forming red colored solutions. The solution in alcohol was used for the staining and dyeing oi wood, paper, and leather. The dye, applied on the materials particularly on paper, was very fast to light. The dyeing on paper was only slightly influenced by 49 hours exposure to the iadometer; several commercial alcohol-solubie dyes were markedly affected in 7 hours of the same exposure.

- Products, having the same general characteristics as the product of Example I, were obtained from the same water soluble dye and di-phenylguanidine-acetate. Similar products were obtained with the use or the hydrochloride of one or more of the following guanidines: di-(o-anisyl) -guanidine, di-(2-ethyl-hexyl) -guanidine, dicyclohexyl guanidine, di benzyl guanidine N phenyl-N'-butyl-guanidine.

Di-ortho-tolyl-guanidine salts of the following additional metalliierous azo dyes were prepared by procedures similar to those described in the preceding examples. The treatments, ending in the isolation of the products as well as the initial form oi. the products, vary. However, in all cases, alcohol soluble solids were finally obtained. All 3i htgiese products showed excellent iastness to Aso combination Metal present :1 c acid.

hen l-pyrazolone l-ch lorono d ol sci l-amino-Q-naphthcl-isullonic acid -0 l-naphthoi-B-suiionio acid i-chloro-2-amino-phenoi-6-suiionic acid 2:4-di-hydmxy-quinoline- Galic clic acid benzidinc -i resort-in 4- 2-smino-pbenol-44ulionic acid): rhoduline ncld...' :sulionic arid beta nsphth powder wassoluble in ethyl alcohol and in amyl alcohol. The solutions were violet colored.

This product was also used in the dyeing and staining of leather, paper, and wood. The treated materials were reddish-violet colored.

The dye was very fast to light. The influence of 56 hours exposure to a iadometer was very slight; on the other hand, 13 hours of similar exposure of a number of commercial dyes of similar type, that had been similarly applied, caused marked losses in strength.

. Example III The can combination, prepared by diazotization of 4-ehloro-2-amino-phenol-6-sulionic acid and subsequent coupling to 1-(4'-sulto-phenol) -8- methyI-B-pyrazolone, was converted to a chromium complex by the procedure described in Example No. I of U. S. P. 1,888,516. The product was isolated in the usual manner.

Six parts of the product was dissolved in 250 parts of water, and, after 0.5 part 0! acetic acid was added, the solution was filtered. The solution was cooled to 5 C. and to it were added parts of an 11% aqueous solution of di-orthotolyl-guanidine hydrochloride. A tacky red substance separated. The supernatant solution was removed by decantation. The tacky product was washed several times with a very dilute solution of di-ortho-tolyl-guanidine hydrochloride. The

The products oi this invention are characterized by their tastness to light. When this property of these colors is compared with the corresponding property of the most practical commercial substituted-guanidine salts of non-metallic dyes giving the same shades, an improvement in light-i'astness oi five to eight times is observed. The dyes are sufllciently soluble in ordinary organic solvent such as alcohol and ethyl acetate and have fine amnity tor the materials which we have named. The shades are good and their resistance to other destructive influences is satisfactory.

As many apparently widely diilerent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. Guanidine (di-substituted from the class oi. radicals consisting of alkyl, aralkyl, aryl and cyclohexyi) salts of metalized azo dyes having at least one acid group from the class consisting of sulionic and carboxy, and having a metal in the range atomic weight from 51.9 to 64.0, inclusive.

2. Di-aryl guanidine salts or metalized azo dyes having at least one acid group from the class consisting oi suli'onic and carboxy, and a metal in the range atomic weight 51.9 to 64.0, inelusive.

3. Dl-arylguanidine salts oi metalized azo dyes having at least one acid group from the class consisting of sulionic and carboxy, and a metal from the group consisting of copper and chromium.

4. Di-ortho-tolyl guanidine salts of metalized azo dyes having at least one acid group i'rom the class consisting oi suli'onic and carboxy, and a metal in the range atomic weight 51.9 to 64.0, inelusive.

5. Diialkoxy-phenyl) guanidine salts 0! metalized azo dyes having at least one acid group from the class consisting of sulfonic and carboxy, and a metal in the range atomic weight 51.9 to 64.0, inclusive.

6. Di-iwlyl guanidine salts of metalized azo dyes having at least one acid group from the Patent No. 2,165,934.

class consisting of sulionic and carbon, and a metal in the range atomic weight 51.9 to 84.0, inclusive.

8. The process which comprises dissolving a water-soluble metaliaed aao dye in neutral aqueous solution, adding thereto an aqueous solution oi guanidine (ii-substituted from the class of radicals consisting of aryl, alkyL'aralkyl, and cyclohexyi, and isolating the product.

9. Diaryl-guanidine salts oi chromiierous ortho-hydroxy-azo compounds, having at least one acid group from the class consisting of suiionic and car-boxy.

10. A di-ortho-tolyl-guanidine salt 0! the chromed dye formed by interacting diazotised 1- amino-2-naphthol-4-sulfonic acid and I-(suliophenyl) -3-methyl-5-pyraaolone.

11. The di-ortho-tolyl-guanidine salts of chromed complexes of ortho-hydroxy-aao dyes,

class consisting of sulionic and carboxy, and a having at least one water-solubilising substltmetal in the range atomic weight 51.9 to 64.0, uent. inclusive. HERBERT W. DAUDT.

'1. Di-ortho-anisyl guanidine salts oi metalized CHESTER W. HANNUM. a o dyes having at least one acid group from the Certificate of Correction July 4, 1939.

HERBERT W. DAUDT ET AL.

It is hereby that errors appear in the printed specification of the above numbered atent requiring correction as follows: Page 1, first column, line 23, after the word ydroxy insert group; page 2, in the table, second column thereof, line ll, for before rhoduline ec1 read 1 and that the said Letters Patent should be read with these corrections therein that record of the case in the Patent Oflice.

Signed and sealed this 12th day of September, A. D. 1939.

. g HENRY VAN ARSDALE,

Acting Commissioner of PM.

the same may conform to the metal in the range atomic weight 51.9 to 64.0, inelusive.

3. Dl-arylguanidine salts oi metalized azo dyes having at least one acid group from the class consisting of sulionic and carboxy, and a metal from the group consisting of copper and chromium.

4. Di-ortho-tolyl guanidine salts of metalized azo dyes having at least one acid group i'rom the class consisting oi suli'onic and carboxy, and a metal in the range atomic weight 51.9 to 64.0, inelusive.

5. Diialkoxy-phenyl) guanidine salts 0! metalized azo dyes having at least one acid group from the class consisting of sulfonic and carboxy, and a metal in the range atomic weight 51.9 to 64.0, inclusive.

6. Di-iwlyl guanidine salts of metalized azo dyes having at least one acid group from the Patent No. 2,165,934.

class consisting of sulionic and carbon, and a metal in the range atomic weight 51.9 to 84.0, inclusive.

8. The process which comprises dissolving a water-soluble metaliaed aao dye in neutral aqueous solution, adding thereto an aqueous solution oi guanidine (ii-substituted from the class of radicals consisting of aryl, alkyL'aralkyl, and cyclohexyi, and isolating the product.

9. Diaryl-guanidine salts oi chromiierous ortho-hydroxy-azo compounds, having at least one acid group from the class consisting of suiionic and car-boxy.

10. A di-ortho-tolyl-guanidine salt 0! the chromed dye formed by interacting diazotised 1- amino-2-naphthol-4-sulfonic acid and I-(suliophenyl) -3-methyl-5-pyraaolone.

11. The di-ortho-tolyl-guanidine salts of chromed complexes of ortho-hydroxy-aao dyes,

class consisting of sulionic and carboxy, and a having at least one water-solubilising substltmetal in the range atomic weight 51.9 to 64.0, uent. inclusive. HERBERT W. DAUDT.

'1. Di-ortho-anisyl guanidine salts oi metalized CHESTER W. HANNUM. a o dyes having at least one acid group from the Certificate of Correction July 4, 1939.

HERBERT W. DAUDT ET AL.

It is hereby that errors appear in the printed specification of the above numbered atent requiring correction as follows: Page 1, first column, line 23, after the word ydroxy insert group; page 2, in the table, second column thereof, line ll, for before rhoduline ec1 read 1 and that the said Letters Patent should be read with these corrections therein that record of the case in the Patent Oflice.

Signed and sealed this 12th day of September, A. D. 1939.

. g HENRY VAN ARSDALE,

Acting Commissioner of PM.

the same may conform to the 

